We performed a combined secondary electron yield (SEY) and x-ray photoelectron spectroscopy study as a function of the electron dose and energy on a Cu technical surface representative of the LHC accelerator walls. The electron bombardment is accompanied by a clear chemical modification, indicating an increased graphitization as the SEY decreases. The decrease in the SEY is also found to depend significantly on the kinetic energy of the primary electrons. When low-energy primary electrons are employed (E≤20 eV), the reduction of the SEY is slower and smaller in magnitude than when higher-energy electrons are used. Consequences of this observation are discussed mainly for their relevance on the commissioning scenario for the LHC in operation at CERN (Geneva), but are expected to be of interest for other research fields.